Naoss



Reissued June 4, 1940 UNITED STATES AZO mms Swanie S. Rossander, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Original No. 2,148,134, dated Febru-- ary 21, 1939, Serial No. 122,011, January 23, 1937. Application for reissue November 28,

1939, Serial No. 306,488

8 Claims.

A. This invention relates to azo dyestuffs and to material of organic fibrous origin dyed with the new dyestuffs, and to processes of producing the dyes and of dyeing.' The invention will be described with reference to particular examples but this description is to be taken as exemplary, not limitative.

B. It is an object of the invention to dye cotton and regenerated cellulose particularly, and also wool, leather, and organic derivatives of cellulose, such as the cellulose esters and ethers, by processes which yield on cotton and regenerated cellulose dyeings of outstanding fastness to washing. Other objects of the invention will be to produce the new dyes and dyed products by processes which are economically and technically satisfactory.

C. The objects of the invention are accomplished, generally speaking, by diazotizing the compounds produced in our copending application Serial Number 122,030, filed of even date herewith, and coupling thereto azo dyestuff developing agents such as beta naphthol, pyrazolone, 2:4-dihydroxy quinollne, meta tolylene diamine, and aceto acetanilide. The objects of the invention are accomplished in a preferred form by dyeing the material with the products of the said identified application, subjecting the dyed fiber to a diazotization process and coupling it to the selected developing agent. Preferred results are sometimes obtained by the use of beta naphthol and l-phenyl-3-rnethyl-5-pyrazolone. It will be found that dyestuffs possessing ortho amino azo groupson the N components are not generally diazotizable and are, consequently, not satisfactory for use in this invention.

D. The invention will be more fully comprehended by reference to the examples, in the table of which the arrows indicate that the preceding compound is diazotiz'ed and coupled to the indicated equivalents of the compounds to which the arrows point. The symbol PAB means paraamino-benzoyl and the symbol MAB means metaamino-benzoyl.

Example 1 Five parts of cotton piece goods were dyed in the usual manner known to those in the art with ten-hundredths part of (l-meta-amino-phenyl- 3-methyl-5-pyrazolone) 2,:Di (para-amino benzoyl) 1:3-diamino benzene-4-sulfonic acid. The dyed fabric (yellow in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three-tenths part or sodium nitrite and four-tenths part of sulfuric acid were added. The whole was stirred "15 minutes and rinsed with cold water. One-tenth part of 1- phenyl-3-methyl-5-pyrazolone was dissolved in 200 cc. water and one-tenth part of soda ash. The solution was stirred rapidly while adding the above rinsed piece goods and then stirred slowly for 15 minutes and rinsed in cold water and dried. The dyeing was a bright greenish yellow in shade. The formula of the dye on the fiber is:

Example II Five parts of cotton piece goods were dyed in the usual manner known to those skilled in the art with two hundredths part of di(para amino benzoyl) meta phenylene diamineIZJ-acidh. The dyed fabric (red in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three tenths part of sodium nitrite and four tenths part of'fsulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of 2- naphthol was dissolved in 200 parts of water and one twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes, rinsed in cold water and dried. The

dyeing was a bright Bordeaux shade. mula of the dye on the fiber is:

The for- N= SOaNa N-NOO ONH Example 1!! Five parts of cotton piece goods were dyed in the usual manner known to those skilled inv the art with two hundredths part of di(meta amino benzoyl) 1 3 diamino benzene 4 sulfonic acid:,(meta amino benzoyl J-acid)z. The dyed fabric (orange in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three tenths part of sodium nitrite and four tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of 2-naphthol was dissolved in 200 parts of water and one twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes, rinsed in cold water and dried. The dyeing was a bright orange shade. The formula of the dye on the fiber is:

SOuNa Example IV Five parts of cotton piece goods were dyed in the usual manner known to those skilled in the art with two hundredths part of di(para amino benzoyl) 1-3-diamino benzene-l-sulfonic acidj (l-meta amino pheny1-3-methyl-5-pyrazolone)2. The dyed fabric (yellow in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three tenths part of sodium nitrite and four tenths part of sulfuric acid were Example V 8 parts of (1-meta-amino-phenyl-3-methyl-5- pyrazolone) ail'dflpara amino benzoyl) 1:3 diamino benzene-4-sulfonic acid were slurried with 300 parts of water. 2 parts of caustic soda were added and warmed to solution and then cooled to 20 C. 2 parts of sodium nitrite were added and the whole was dumped in Sparts of hydrochloric acid and stirred for 3 hours, maintaining GONE-7 acidity to Congo red and a distinct excess of sodium nitrite. v

5 parts of beta naphth'ol were slurried with 200 parts of water. Approximately 1.4 parts of caustic soda were added and warmed to solution, distinctly alkaline to brilliant yellow paper.

The whole was cooled to 20 C. 10 parts of soda ash were added and stirred until dissolved. The

tetrazdprepa-red in the above paragraph was slowly added and the mass stirred three hours, maintaining a distinct excess of beta naphthol and alkalinity on brilliant yellow paper.

The whole was warmed to C., filtered, and dried at LO-smm -100 C. The dried powder was yellow. The

formula of the dye is:

Example VII Five parts of cotton piece goods were dyed in Example VI 11 parts of (para-amino-benzoyl J-acidn; di(para-amino-benzoyl) 1:3-diamino benzene-4- suli'onic acid were slurred with 300 parts of water. 2 parts of caustic soda wereadded and warmed until dissolved. The whole was cooled to 20 C. and 2 parts of sodium nitrite were added. The mass was dumped in 5 parts of hydrochloric acid and stirred for 3 hours, maintaining an acidity to Congo'red and distinct excess of sodium nitrite.

5 parts of 1-phenyl-3-methyl-5-pyrazolone soda were slurried and stirred at 20 C. until dissolved. 10 parts of soda ash were added and stirred until dissolved. The tetrazo prepared in the above paragraph was slowly added. The mass was the usual manner known to those in the art with four-hundredths part of (para-amino-benzoyl J-acidhtzdi (para-amino-benzoyl) 1:3-diamino benzene-4-sulfonic acid. The dyed fabric (orange in shade) Was rinsed in cold Water and put in a casserole with 200 parts of water at 20 C. Threetenths part of sodium nitrite and four-tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of Z-naphthol was dissolved in 200" parts water and one twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes, rinsed in cold water and dried. The dyeing was a bright orange shade. The formula of the dye is:

5 OaNa 0 I II 9 NBC o-ON=N-gcom In the following tables precedures similar to the foregoing were employed.

pling components comprise benzene, naphthalene, pyrazolones, quinolineor aceto acetanilide Diazo component Coupling component Shade on cotton Beta naphthol Orange. 8 Di(pata-amino-benzoyl) 1:3-diamino benzene kphtgnyl-i-metgyl-S-pyrazolone Scu ls. ee ace am e 0. I fiegahtoylene diamilzilg Bull scarlet.

: 1 y roxy qulno e range. 9 Di(para-amino-benzoyl) 1:3-diamino benzene ((meta-ar'nino-benzoyl) J acid), Beta mphthol 10 Di(para-amino-benz0yl) 1:3-diamino benzene d B d i o or eaux. (J-ac1d): 11 Di(Dara-aminc-benzoyl) 1:3-diamino benzene do Orange, i(l-meta-amino-phenyl-5-pyrazolonc-3-carbcxylic acid)| 4phenul-3-n1ethyl-5-pyrazolone Yellow. Beta na hthol Orange. 12 Di(para-amino-benzoyl) 1:3-diamino benzene 1-phony-3-methyl-5- yramlone Yellow.

I ((para-am1no-benzoyl) J-acid) (l-meta-amino-phenyl-5-pymzol0ne-3- 2-4 dlhydrox qulnoline Do. catboxylic acid) lidetta, phetlxyfinie dlamlne SYellow brown. oe ace n 1 e e ow. 2o 13 Di(para-amino-benzoyl) 1:3-diamino benzene 0 (Di(para-amino-benzoyl) 3:5-diamino we J -acid),. Beta naphtho] range 14 Di(para-amino-benzoyl) 1:4-diamino benzene d B d o or eaux.

J -ac1d 15 Di(para-amino-benzoyl) 1:4-diamino naphthalene ((meta-amino-benzoyl) I-acid);

16 Di(para-amino-benzoyl) lA-diamino naphthalene 3((para-amino-benzoyl) J-acid), 17 Di(para-amino-benzoyl) 1:4diamino naphthalene Beta naphtha (1-meta-amino-phenyl-5-pyrazolone-B-catboxylic acid); 1-phenyl-3-methyl-5-pyrazolone Yellow. Beta naphthol Orange. 18 Di(para-amino-benzoyl)1:3-diaminobenzene-l-sulfonic acid iA-dihydrozq;1 diuinol' V Yella'gw.

g (1-meta-amino-phenyl-Smyrazolone-B-carboxylic acid): i%?i g1jgigmi5h Y u gzb y} e ao y ene am e e ow town. 19 Di(pata-amino-henzoyl) 1:3-diamino benzene-d-sulfonic acid ((meta-amino'benzoyl) I-acid), Beta uaphtho] Orange 20 Di(para-amino-benzoyl) 1:3-diamino benzene-*l-sulfonic acid d D ((para-amino-henzoyl) J -ac1d)= .c

. Beta na htholnfl, Orange; 21 Di(para-amino-benzoyl) lza-diamino beuzenel-sulfonic acid kpheny -3-m3tlyl-5- Yellgw.

g (l-meta-amino-phenyl-3-methyl-S-pyrazolone)i fg gfgg i g fiai E Meta pheny ene diamin Yellow brown. 22 Di(para-amino-benzoyl) 1:3-diamino henzenet-sulfonic acid (l-meta-amino-pheny -5-pyrazolone-3-carboxylic acid) ((para-amino- Beta naphthol v Orange. benzoyl) .T-acid) 23 D1(para-amino-benzoyl) mine benzene4-su1ionica d D (meta toluldme), 24 Di(para-amino-bcnzoyl) 1:3-diamino bcnzeneA-sulfonic acid- D i (Di(para-amino-benzoyl) 3:5-diamino benzoylJ-acidh.-.

25 Di(para-amino-benzoyl) 1:3-diar'nino bcnzene4-sulfonic acid 3 Y n (Di(para-amino-benzoyl) 3:5-diamino benzoyl J-acid); m e ow orange 26 Di(para-amino-benzoyl) 1:4-diamino benzene-5-sulfonic acid ((para-amino-benzoyl) Lacid), Beta h Orange 5 27 Di(para-amino-benzoyl) 1:4-diamino benzene-E-sullonic acid ((metaa1ninobenzo l I (1 4 v y) -a0 )1 28 Di(pa1 a-amino-benzoyl) lA-damino benzcne-5sulfonic acid Beta naphtha]; (l-meta-amino-phenyl-5-pyrazolone4carboxylic acid);.- 1-phenyl-3-methyl-fi-pyrazolone Yellow.

29 Di(para-amino-benzoyl) 1:4-dian1ino benzene-5-s ulfonic acid Beta naphtho] Olmsm (1-meta-aniino-phonyl-S-methyl-5-pyrazolone)g 1-phenyl-3-methyl-5-pyrazolone Yellow.

30 Di(para-amino-benzoyl) 1:4-diamin0 benzene-5-sulfonic acid Beta naphthol Bordeaux. I

31 Di(meta-amino-benwyl) 1:3-diamino benzene-4-sulfonic acid O ((rneta-alnino-benzoyl) J-acidh; "T range 32 ,Di(meta-amino-bcnz.oyl) 1:3-diamino benzene-4-sulfonic acid do Do.

((pai'a-almno-benzoyl) J-acld):

Beta na hthol Orange. 33 Di(meta-amino benzoyl) 1:3-diamino bcnzene--sultonic acid l-pheny -3-Inethyl-5-lpyrazolone Yellow. 3(I-meta-amino-phenyl-5-pyrazoloneS-carboxylic acid): Fggfigf Et g8: Illa/ eta phefiglelne mini-3.. lged brown. eta na 9 range. 34 Di(rneta-an1ino-benzoyl) 1:3-diamino benzene-4-sulfonic acid Meta to ylene.%ia1mgine l gcg brown. 2 (1-meta-amino-phenyl-ii-methyl-fv-pyraeolono)a fi1ggigggff e :58:

ce 0 we an] 1 e 35 Di(pa1-a-amino-benzoyl) 1:3-diamino benzenc-4-sulfonic acid Beta m hthol orange (l-meta-an1ino-phenyl-5-py-razolone-Il-cal-boxylic acid) I l-pheny-3-methyl-5-pyrazolone Yellow. 36 Di(para-amino-benzoyl) 1:3-diamino benzeneu Beta naphthol 0range bhmeta-amino-phenyl-S-pyrazolone-a carboxylic acid); 1-phenyl-3-methyl-5-pyrazolone Yellow.

F. The products of the invention may be Tl. produced on the fiber or in isolated form. Counuclei in which coupling takes place adjacent to an hydroxy or amino group. The

azo components-are represented by theformulaf:

in which R comprises a benzene nucleus, R1

naphthalene or pyrazolone nuclei. G. There may be substituted on the various nuclei of the invention substituent groups from the list alkyl, alkoxy, halogen, aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy, trifluoro-alky, 'hydroxy, sulfonic acid and carboxyl.

H. The preferred products, when applied by diazotization and development on the fiber, produce dyeings of outstandingfast'ness'to'washing and of exceptionab discharge properties.

comprise aryl nucleifan'd R2 comprise benzene,

departing from the spirit and scope thereof, it is to be understoodthat I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. The compound represented by the formula:

-C O NII- Y 3. The compound represented by the formula:

50 The dyes are frequently used in the form of their alkali metal salts.

I. As many apparently widely different embodiments 01 this invention may be made without N==N BOINB 4. The compound represented by the formula:

Naols- N=N H0 NEG OON=N 5. A material of organic fibrous origin dyed with the product represented by the formula:

a 6. A material of organic fibrous origin dyed with the product represented by the formula:

- pyrazolone-3carb0'xyI, each E is the radical of an azo dyestufi coupling component, from the N=N SOSNB NBC 0- 7. A material of organic fibrous origin dyed class consisting .of those having benzene, naph with the product represented by the formula: thalene, pyrazolone, quinoline and acetoacet- NHO cOnaw-manilide nuclei, and Y-is-one of a group consisting of hydrogen and sulfonic acid.

8. A material of organic fibrous origin dyed with the product represented by the formula:

SVVANIE S. ROSSANDER. 

